CN101433840B - Carbon nano-tube microparticle supported palladium nano particle as well as preparation method and application thereof - Google Patents
Carbon nano-tube microparticle supported palladium nano particle as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN101433840B CN101433840B CN2007101772112A CN200710177211A CN101433840B CN 101433840 B CN101433840 B CN 101433840B CN 2007101772112 A CN2007101772112 A CN 2007101772112A CN 200710177211 A CN200710177211 A CN 200710177211A CN 101433840 B CN101433840 B CN 101433840B
- Authority
- CN
- China
- Prior art keywords
- cnt
- particulate
- nano particle
- supported palladium
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to carbon nano-tube particles for supporting palladium nano-particles, a preparation method thereof, and application of the carbon nano-tube particles (as a catalyst) for supporting the palladium nano-particles in a Suzuki cross-coupling reaction. Sodium chloropalladate, multi-walled carbon nanotube particles, sodium dodecyl sulfate and glycol are taken as reactants, and are stirred to react at a temperature of between 110 and 140 DEG C to obtain the carbon nano-tube particles with the palladium nano-particles supported on the surfaces of multi-walled carbon nanotubes, and the carbon nanotube particles are assembled and formed by numerous multi-walled carbon nanotubes which are entangled with one another. The carbon nano-tube particles for supporting the palladium nano-particles have rich mesopores as well as larger specific surface area and pore volume, and supported palladium has the characteristics of small grain diameter, even distribution and so on, thereby having excellent catalytic effect. The carbon nano-tube particles for supporting the palladium nano-particles also have good structural stability, are easy to separate from organic media, and can be taken as the catalyst for the Suzuki cross-coupling reaction.
Description
Technical field
The invention belongs to the nano material preparation technical field, CNT particulate of particularly a kind of supported palladium nano particle and preparation method thereof, and the CNT particulate of this supported palladium nano particle is as the application of catalyst in the Suzuki cross-coupling reaction.
Background technology
Palladium has application widely as a kind of noble metal in chemistry, chemical catalysis field.Yet because the reunion effect of metal nanoparticle, the monodispersed ultra-fine palladium metal nano particle of controlled preparation is difficulty comparatively.So, general processing method is that it is carried on a certain carrier, as Srividhya Kidambi, and Jinhua Dai, Jin Li, and Merlin L.Bruening, J.Am.Chem.Soc.2004,126,2658, and Yijun Jiang and Qiuming Gao J.Am.Chem.Soc.2006,128,716 are introduced.Owing to have characteristics such as high specific area, good electrical conductivity and light weight, CNT might be widely used as the carrier of catalyst.
Summary of the invention
One of purpose of the present invention provides the CNT particulate of the supported palladium nano particle that is applied to the stable, efficient of Suzuki cross-coupling reaction and is easy to separate.
Two of purpose of the present invention provides the method for the CNT particulate of the preparation supported palladium nano particle that a kind of technology is simple, cost is low.
Three of purpose of the present invention provides the CNT particulate of supported palladium nano particle as the application of catalyst in the Suzuki cross-coupling reaction.
The CNT particulate of supported palladium nano particle of the present invention is to be entangled with each other and to be assembled and constitute by numerous multi-walled carbon nano-tubes, therefore has the passage that higher specific surface area and numerous Gong reactant and product pass through; Load has Pd nano particle on the multi-wall carbon nano-tube tube-surface, and the particle diameter of described Pd nano particle is 2～3 nanometers, and preferable particle size is 2.5 nanometers; The particle diameter of the CNT particulate of supported palladium nano particle is 5～25 microns.The particle loaded Pd nano particle of this CNT has higher structural stability, can recycle.
Have abundant mesoporously on the CNT particulate of described supported palladium nano particle, mesoporous aperture is 1～30 nanometer.
The present invention is that lauryl sodium sulfate and ethylene glycol are reactant with chlorine palladium acid sodium, multi-walled carbon nano-tubes particulate, and under 110～140 ℃ of conditions, ethylene glycol and chlorine palladium acid sodium generation redox reaction obtain the CNT particulate of supported palladium nano particle.
The preparation method of the CNT particulate of supported palladium nano particle of the present invention may further comprise the steps:
1) amount that adds reactant is to be benchmark with 5 milligrams of multi-walled carbon nano-tubes particulates; Get 5 milligrams of multi-walled carbon nano-tubes particulates, 400～500 milligrams of lauryl sodium sulfate are dissolved in 20 milliliters of ethylene glycol, and the dispersion liquid that forms homogeneous is stirred in ultrasonic dispersion;
2) be that 55～60 microlitre chlorine palladiums acid sodium of 0.1 mol joins in the dispersion liquid that step 1) obtains with concentration,, obtain the black solid sediment at 110～140 ℃ of following stirring reactions;
3) with step 2) centrifugation of black solid sediment, the washing that obtain;
4) product that step 3) is obtained is not less than 10 hours 50～70 ℃ of vacuum drying, can obtain the pattern CNT particulate of supported palladium nano particle preferably.
Preparation method's mechanism of the CNT particulate of supported palladium nano particle provided by the invention is as follows: multi-walled carbon nano-tubes particulate and lauryl sodium sulfate are added in the ethylene glycol, add thermal agitation, purpose is lauryl sodium sulfate is dissolved in ethylene glycol fully and to form CNT dispersion liquid than homogeneous.Dropwise add chlorine palladium acid sodium then, purpose is that chlorine palladium acid sodium can evenly be disperseed in solution, and it is too high to be unlikely to local concentration.Keep stirring reaction to carry out more than 3 hours down at 110～140 ℃, can obtain the CNT particulate of supported palladium nano particle.With sample centrifugation, washing, vacuum drying is more than 10 hours under 50～70 ℃ of conditions at last.
Have abundant mesoporous, bigger specific area and pore capacities on the CNT particulate of supported palladium nano particle of the present invention, it is little that the palladium of load has a particle diameter, and therefore characteristics such as be uniformly dispersed have excellent catalytic effect.The CNT particulate of these supported palladium nano particles also has good structural stability, is easy to separate from organic media, can be used as good organic reaction catalyst.
The CNT particulate of supported palladium nano particle of the present invention can be as Suzuki cross-coupling (phenyl boric acid and iodobenzene etc.) catalyst for reaction, and has good catalytic effect.
The CNT particulate of supported palladium nano particle of the present invention is as the catalyst of Suzuki cross-coupling reaction the time, catalytic reaction is easy to separate from reaction system by conventional separation method (as centrifugation, filter paper filtration etc.) after finishing, and therefore can recycle.
Multi-walled carbon nano-tubes particulate of the present invention can be prepared by polypropylene, imvite, nickel formate.By the amount of control chlorine palladium acid sodium and lauryl sodium sulfate, can obtain being entangled with each other and assembling the CNT particulate of the supported palladium nano particle that constitutes by numerous multi-walled carbon nano-tubes.
The CNT particulate of the supported palladium nano particle that the present invention makes is to be entangled with each other and the micro particles that is assembled into by numerous multi-walled carbon nano-tubes, they have higher specific surface area, countless passages are provided not only for reactant and product, and be easy to separate from reaction system by conventional method, can reach the separation purpose such as filtering by centrifugation, filter paper.Therefore, we are carried on Pd nano particle on the CNT particulate, make it not only have good catalytic effect, and are easy to separate from product after catalytic reaction is finished.Through the experiment of Suzuki cross-coupling reaction, confirm that the catalyst that we prepare has good catalytic effect and stability really, and be easy to from reaction system, separate and recycle.
Preparation method's technology of the present invention is simple, cost is low, the CNT particulate of the supported palladium nano particle that makes has abundant mesoporous, good structural stability, higher specific surface area, its Pd nano particle has high catalytic activity, has important use value aspect the organic catalytic reaction (as the Suzuki coupling reaction).
Description of drawings
The CNT particulate of the supported palladium nano particle that Fig. 1 embodiment of the invention 1 the makes last X-ray diffractogram of pulverizing.
The stereoscan photograph of the CNT particulate of the supported palladium nano particle of Fig. 2 embodiment of the invention 1 and 2 preparations.
The transmission electron microscope photo of the CNT particulate of the supported palladium nano particle of Fig. 3 embodiment of the invention 1 is wherein:
Fig. 3 a is adding lauryl sodium sulfate, the transmission electron microscope photo of the CNT of the supported palladium nano particle that CNT particulate, chlorine palladium acid sodium make after reaction in the presence of the ethylene glycol.
Fig. 3 b is the particle diameter distribution map of the Pd nano particle that obtains.
When Fig. 4 Comparative Examples 1 does not add lauryl sodium sulfate, the transmission electron microscope photo of the CNT of the supported palladium nano particle that CNT particulate, chlorine palladium acid sodium make after reacting in the presence of ethylene glycol.
The photo of common filter paper separating catalyst of Fig. 5 embodiment of the invention 5 usefulness and product.
The specific embodiment
5 milligrams of CNTs and 402 milligrams of purity being not less than 99% lauryl sodium sulfate adds in 20 milliliters of ethylene glycol, added thermal agitation 30 minutes, ultrasonic then 1 hour, dropwise add 55 microlitre chlorine palladium acid sodium aqueous solutions (chlorine palladium acid na concn is 0.1 mol), 110 ℃ were heated stirring reaction 3 hours down.Taking-up is left standstill after a period of time to solid sediment and is occurred, and centrifugation is 10～15 minutes under 4000 rev/mins condition, uses distilled water and ethanol washing sample then, repeats 3～5 times.The sample that makes at last vacuum drying more than 10 hours under 50～70 ℃ of conditions, the CNT particulate of the supported palladium nano particle of the black that obtains, as shown in Figure 2.The dried sample that takes a morsel is dispersed in the ethanol again, and at 120W, ultrasonic dispersion is 5 minutes under the ultrasonic wave condition of 40KHz, and point sample is used transmission electron microscope and scanning electron microscopic observation afterwards in the copper mesh that is used for transmission electron microscope.Fig. 1 for the CNT particulate behind the supported palladium nano particle through the last X-ray diffractogram that records of pulverizing.In 2 θ=26.5 °, 43.2 ° and 40.1 °, 46.7 °, 68.7 ° of diffraction maximums of locating correspond respectively to the diffraction maximum of graphitic carbon and the diffraction maximum of simple substance palladium.Fig. 2 is the stereoscan photograph of the CNT particulate of supported palladium nano particle, and as seen, the particle diameter of the CNT particulate of supported palladium nano particle is at 5～25 microns.The CNT particulate is to be entangled with each other and to be assembled by numerous multi-walled carbon nano-tubes to constitute, and has abundant mesoporously on the CNT particulate of supported palladium nano particle, and mesoporous aperture is 1～30 nanometer.Fig. 3 a is the transmission electron microscope photo of the CNT of supported palladium nano particle, and the average grain diameter of the Pd nano particle on the CNT particulate of the supported palladium nano particle that obtains is at 2.7 nanometers (Fig. 3 b).
Embodiment 2
Take by weighing 5 milligrams of CNT particulates, drip 60 microlitre chlorine palladium acid sodium aqueous solutions, other condition gets the CNT particulate of supported palladium nano particle with embodiment 1.The transmission electron microscope photo shows that the average grain diameter of Pd nano particle is 3 nanometers.
Weigh 5 milligrams of CNT particulates, add 500 milligrams of lauryl sodium sulfate, other condition makes the CNT particulate of supported palladium nano particle with embodiment 1, and the average grain diameter of Pd nano particle is 3 nanometers.
Weigh 5 milligrams of CNT particulates, add 500 milligrams of lauryl sodium sulfate, 20 milliliters of ethylene glycol, it is 0.1 mol chlorine palladium acid sodium aqueous solution that ultrasonic dispersion back adds 55 microlitre concentration, but the reaction time is 10 hours, obtain the CNT particle catalyst of supported palladium nano particle at last, wherein the average grain diameter of Pd nano particle is 2.7 nanometers.
Comparative Examples 1
Get 5 milligrams of CNTs and add in 20 milliliters of ethylene glycol, added thermal agitation 30 minutes, ultrasonic then 1 hour, dropwise add 55 microlitre chlorine palladium acid sodium aqueous solutions (chlorine palladium acid na concn is 0.1 mol), 110 ℃ were heated stirring reaction 3 hours down.Taking-up is left standstill after a period of time to solid sediment and is occurred, and centrifugation is 10～15 minutes under 4000 rev/mins of conditions, uses distilled water and ethanol washing sample then, repeats 3～5 times.The sample that makes at last vacuum drying more than 10 hours under 50～70 ℃ of conditions, the CNT particulate of the supported palladium nano particle of the black that obtains.The dried sample that takes a morsel is dispersed in the ethanol again, and at 120W, ultrasonic dispersion is 5 minutes under the ultrasonic wave condition of 40KHz, and point sample is used transmission electron microscope and scanning electron microscopic observation afterwards in the copper mesh that is used for transmission electron microscope.Fig. 4 is the transmission electron microscope photo of the CNT of supported palladium nano particle.As seen, Pd nano particle size and skewness on the CNT particulate of the supported palladium nano particle that obtains, average grain diameter is about 10 nanometers.
Embodiment 5
Make the catalyst of Suzuki coupling reaction with the CNT particulate of supported palladium nano particle of the present invention.The catalyst that obtains among right-iodobenzene ethyl ketone (15 mM), phenyl boric acid (20 mM), anhydrous phosphoric acid potassium (40 mM), absolute ethyl alcohol (50 milliliters), the 30 milligrams of embodiment 1 is put in 100 milliliters of round-bottomed flasks, mixture added hot reflux 2 minutes, the portion of product unreacted in addition of testing after 10 minutes.Add hot reflux testing identity reactant complete reaction after 30 minutes again, the reactant liquor cool to room temperature.A large amount of white solids appear in the solution, after adding 50 milliliters of ethyl acetate, with filter paper filtering catalyst and insoluble salt.Separator ethyl acetate on the filter paper, water and ethanol clean and obtain catalyst (Fig. 5).Isolated catalyst is used for next circulation catalytic test.Filtrate is evaporated in vacuum environment and is obtained white solid product, uses ethyl acetate extraction after following white solid product and water mixing.Acetic acid ethyl acetate extract sodium hydroxide solution and salt water washing, and use dried over sodium sulfate, filter.The evaporation of acetic acid ethyl ester obtains white solid product 2.9 grams again in vacuum environment, and productive rate is 98.6%, and molten point is 119.5～124 ℃.Nuclear magnetic data determines that it is products therefrom.Above experimentation repeats 4 times again, reuses after the catalyst separation.Gained distich ethyl benzoate product productive rate is respectively 98.6%, 99.5%, 100%, 98.6%, 98%, illustrate that this catalyst activity is fine, and stability is also fine, and the result as shown in Table 1.
Table one
| Project | Substrate | Period | Output (%) |
| 1 2 3 4 5 | Right-iodobenzoic acid ethyl ester+phenyl boric acid is right-and iodobenzoic acid ethyl ester+phenyl boric acid is right-iodobenzoic acid ethyl ester+phenyl boric acid is right-and iodobenzoic acid ethyl ester+phenyl boric acid is right-iodobenzoic acid ethyl ester+phenyl |
1 2 3 4 5 | 98.6 99.5 100 98.6 98 |
Embodiment 6
The CNT particulate of supported palladium nano particle of the present invention is to the catalytic action of different substrates.With right-iodobenzoic acid ethyl ester or right-iodobenzene ethyl ketone (15 mM), phenyl boric acid (30 mM), anhydrous phosphoric acid potassium (60 mM), absolute ethyl alcohol (50 milliliters), the catalyst that obtains among 30 milligrams of embodiment 1 is put in 100 milliliters of round-bottomed flasks, mixture added hot reflux 2 minutes, and after 10 minutes (or 30 minutes), silica gel is crossed the pillar right-iodobenzoic acid ethyl ester of proof (or right-iodobenzene ethyl ketone) complete reaction.The reactant liquor cool to room temperature, with filter paper separating solids and liquid.Catalyst cleans with the second alcohol and water after filter paper separates.Filtrate is used ethyl acetate extraction, follow the acetic acid ethyl acetate extract wet chemical, salt solution cleans, use anhydrous sodium sulfate drying then, filter, evaporation obtains semi-solid product 3.72 grams in a vacuum, and the chromatography separation obtains 3.05 gram grease at last, grease slowly becomes white solid at last, and molten point is 46～48 ℃ (seeing Table two).Nuclear magnetic data proves that it is the compound that need obtain, and the results are shown in Table two.
Table two
| Project | The iodobenzene that different groups replace | Phenyl boric acid | Reaction time | Product | Productive rate (%) |
| 1 2 | Right-iodobenzoic acid ethyl ester is right-the iodobenzene ethyl ketone | The phenyl boric acid phenyl boric acid | 10 minutes 30 minutes | 4-Ethyl formate biphenyl 4-biphenyl ethyl ketone | 90 98.6 |
Claims (7)
1. the CNT particulate of a supported palladium nano particle, it is characterized in that: described CNT particulate is to be entangled with each other and to be assembled by numerous multi-walled carbon nano-tubes to constitute, load has Pd nano particle on the multi-wall carbon nano-tube tube-surface, has mesoporous on the CNT particulate of described supported palladium nano particle;
The particle diameter of described Pd nano particle is 2～3 nanometers;
The particle diameter of the CNT particulate of described supported palladium nano particle is at 5～25 microns;
Described mesoporous aperture is 1～30 nanometer.
2. the CNT particulate of supported palladium nano particle according to claim 1 is characterized in that: the particle diameter of described Pd nano particle is 2.5 nanometers.
3. the preparation method of the CNT particulate of a supported palladium nano particle according to claim 1 and 2, it is characterized in that: with chlorine palladium acid sodium, multi-walled carbon nano-tubes particulate, lauryl sodium sulfate and ethylene glycol are reactant, stirring reaction under 110～140 ℃ of conditions obtains the CNT particulate of supported palladium nano particle.
4. method according to claim 3 is characterized in that: the preparation method of the CNT particulate of described supported palladium nano particle may further comprise the steps:
1) amount that adds reactant is to be benchmark with 5 milligrams of multi-walled carbon nano-tubes particulates; Get 5 milligrams of multi-walled carbon nano-tubes particulates, 400～500 milligrams of lauryl sodium sulfate are dissolved in 20 milliliters of ethylene glycol, and the dispersion liquid that forms homogeneous is stirred in ultrasonic dispersion;
2) be that 55～60 microlitre chlorine palladiums acid sodium of 0.1 mol joins in the dispersion liquid that step 1) obtains with concentration,, obtain solid sediment at 110～140 ℃ of following stirring reactions;
3) with step 2) the solid sediment centrifugation, the washing that obtain;
4) product that step 3) is obtained is not less than 10 hours 50～70 ℃ of vacuum drying, obtains the CNT particulate of supported palladium nano particle.
5. method according to claim 4 is characterized in that: described to join chlorine palladium acid sodium in the dispersion liquid that step 1) obtains be dropwise to add chlorine palladium acid sodium.
6. according to claim 3 or 4 described methods, it is characterized in that: described 110～140 ℃ of following stirring reaction times more than 3 hours.
7. the purposes of the CNT particulate of a supported palladium nano particle according to claim 1 and 2 is characterized in that: the CNT particulate of described supported palladium nano particle, and can be as the catalyst of Suzuki cross-coupling reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101772112A CN101433840B (en) | 2007-11-12 | 2007-11-12 | Carbon nano-tube microparticle supported palladium nano particle as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101772112A CN101433840B (en) | 2007-11-12 | 2007-11-12 | Carbon nano-tube microparticle supported palladium nano particle as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101433840A CN101433840A (en) | 2009-05-20 |
| CN101433840B true CN101433840B (en) | 2011-02-16 |
Family
ID=40708569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101772112A Expired - Fee Related CN101433840B (en) | 2007-11-12 | 2007-11-12 | Carbon nano-tube microparticle supported palladium nano particle as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101433840B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104759293B (en) * | 2015-03-09 | 2017-09-29 | 浙江工业大学 | A kind of load type palladium catalyst and its preparation and application using nano-sized carbon as carrier |
| KR20180122319A (en) * | 2016-01-15 | 2018-11-12 | 니폰 제온 가부시키가이샤 | A composition for a thermoelectric conversion element, a method for producing a carbon nanotube on which metal nanoparticles are supported, a molded article for a thermoelectric conversion element, a method for producing the same, |
| CN108201897A (en) * | 2018-02-01 | 2018-06-26 | 黑龙江省科学院石油化学研究院 | The method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts |
| CN109395719B (en) * | 2018-11-05 | 2021-10-12 | 江苏大学 | Method for controllably loading noble metal nano material on surface of multi-walled carbon nanotube |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424149A (en) * | 2002-12-27 | 2003-06-18 | 浙江大学 | Method for coating mono-metal particles on carbon nano tube surface |
-
2007
- 2007-11-12 CN CN2007101772112A patent/CN101433840B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424149A (en) * | 2002-12-27 | 2003-06-18 | 浙江大学 | Method for coating mono-metal particles on carbon nano tube surface |
Non-Patent Citations (5)
| Title |
|---|
| Byunghoon Yoon，Chien M. Wai.Microemulsion-Templated Synthesis of Carbon Nanotube-Supported Pd and Rh Nanoparticles for Catalytic Applications.《Journal of the American Chemical Society》.2005,第127卷(第49期),17174－17175. * |
| H.B.Pan,C.H.Yen,B.Yoon,M.Sato,C.M.Wai.Recyclable and Ligandless Suzuki Coupling Catalyzed by Carbon Nanotube-Supported Palladium Nanoparticles Synthesized in Supercritical Fluid.《Synthetic Communications》.2006,第36卷(第23期),3473-3478. * |
| Q.H.Yang，P.X.Hou，S.Bai，M.Z.Wang，H.M.Cheng.Adsorption and capillarity of nitrogen in aggregated multi-walled carbon nanotubes.《Chemical Physics Letters》.2001,第345卷(第1－2期),18－24. * |
| Y.Wang，X.Xu，Z.Q.Tian，Y.Zong H.M.Cheng |
| Y.Wang,X.Xu,Z.Q.Tian,Y.Zong,H.M.Cheng,C.J.Lin.Selective Heterogeneous Nucleation and Growth of Size-Controlled Metal Nanoparticles on Carbon Nanotubes in Solution.《Chemistry-A European Journal》.2006,第12卷(第9期),2542-2549. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101433840A (en) | 2009-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gao et al. | Ni nanoparticles supported on graphitic carbon nitride as visible light catalysts for hydrolytic dehydrogenation of ammonia borane | |
| Liu et al. | Effective reduction of 4-nitrophenol with Au NPs loaded ultrathin two dimensional metal-organic framework nanosheets | |
| Jebali et al. | Cationic cellulose nanofibrils as a green support of palladium nanoparticles: catalyst evaluation in Suzuki reactions | |
| US7396795B2 (en) | Low temperature preparation of supported nanoparticle catalysts having increased dispersion | |
| CN101973518B (en) | Method for preparing nano gold-graphene oxide nano composite material | |
| CN101219378A (en) | Process for producing direct methanol fuel cell electro-catalyst | |
| CN101433840B (en) | Carbon nano-tube microparticle supported palladium nano particle as well as preparation method and application thereof | |
| Wang et al. | In situ synthesis of Ag–Fe3O4 nanoparticles immobilized on pure cellulose microspheres as recyclable and biodegradable catalysts | |
| Hamzavi et al. | Preparation and characterization of a novel spherical cellulose–copper (II) oxide composite particles: as a heterogeneous catalyst for the click reaction | |
| Yang et al. | Controllable synthesis of multiheteroatoms co-doped hierarchical porous carbon spheres as an ideal catalysis platform | |
| CN102847533A (en) | Microwave method for synthesizing attapulgite and palladium nanocomposite catalyst | |
| CN102179526B (en) | Method for preparing cubic crystal nano silver material by oil-water interface method | |
| Sun et al. | Nitrogen-doped carbon supported ZnO as highly stable heterogeneous catalysts for transesterification synthesis of ethyl methyl carbonate | |
| CN110368928A (en) | A kind of catalyst and its preparation method and application for benzyl alcohol oxidation synthesizing benzaldehyde | |
| CN103274441A (en) | Method for preparing nanoscale sheet cerium oxide by hydrothermal method | |
| CN110420662A (en) | It is a kind of can efficient degradation stalk cellulose at low temperature composite catalyzing material and the preparation method and application thereof | |
| CN102847555B (en) | Polymer supported Pd-Ni-B nano-catalyst, preparation method and application thereof | |
| Chang et al. | Electron-modulating effects of intercalating molecules in functionalized graphene oxide: Optimizing the coordination microenvironment of Ag nanoparticles for efficient catalytic A3 coupling reactions | |
| CN102888028B (en) | Method for preparing chitosan-ferroferric oxide (CS-Fe3O4) composite nanoparticles by self-assembly | |
| CN106238080A (en) | The method that p-doped porous graphene and preparation method thereof aoxidizes with catalysis benzylamine | |
| CN1966586A (en) | Reactive, monodispersed surface modified silver nanoparticle and its preparation method | |
| CN102728389B (en) | Preparation method for FePt/graphene composite nano-material | |
| CN102133644B (en) | Method for preparing nickel nano particles | |
| CN104925870A (en) | Solvothermal method for preparing nano-grade ferroferric oxide | |
| Askarisarvestani et al. | Pt@ metal–organic framework (ZIF-8) thin films obtained at a liquid/liquid interface as anode electrocatalysts for methanol fuel cells: different approaches in the synthesis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110216 Termination date: 20141112 |
|
| EXPY | Termination of patent right or utility model |